CN114015007B - Fluorine-containing polyurethane single-ion polymer electrolyte membrane and preparation method and application thereof - Google Patents
Fluorine-containing polyurethane single-ion polymer electrolyte membrane and preparation method and application thereof Download PDFInfo
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Abstract
A fluorine-containing polyurethane single-ion polymer electrolyte membrane and a preparation method and application thereof relate to the technical fields of organic high-molecular functional materials and electrochemistry. The invention aims to solve the problems that the traditional single-ion polymer electrolyte cannot have both lower glass transition temperature and higher lithium ion concentration and cannot have excellent ion conductivity and mechanical property. The method comprises the following steps: adding m-carboxyl lithium benzenesulfonate and polyethylene oxide into a solvent, reacting for 12-94 h, and carrying out vacuum water removal treatment to obtain a reactant a; adding reactant a, perfluoroalkyl-containing diamine and diisocyanate into a solvent, reacting for 12-94 h, and then washing with water, washing with alcohol and drying to obtain fluorine-containing polyurethane single-ion polymer electrolyte; adding the fluorine-containing polyurethane single-ion polymer electrolyte membrane into a solvent, and performing film forming treatment to obtain the fluorine-containing polyurethane single-ion polymer electrolyte membrane. The invention can obtain the fluorine-containing polyurethane single-ion polymer electrolyte membrane, and the preparation method and the application thereof.
Description
Technical Field
The invention relates to the technical field of organic high molecular functional materials and electrochemistry, in particular to a novel fluorine-containing polyurethane single-ion polymer electrolyte membrane and a preparation method thereof, and relates to application thereof in an all-solid-state lithium ion secondary battery.
Background
As energy demand increases, the conflict between energy demand and supply is becoming more acute. The lithium secondary battery has advantages of high specific energy and energy density, and plays an irreplaceable role in energy storage devices. At present, liquid lithium ion batteries widely used in commerce mainly comprise a positive electrode, a negative electrode, a microporous diaphragm, a liquid electrolyte and the like. However, the lithium-ion battery has potential safety problems, dendritic lithium dendrites are easy to generate, dead lithium is even generated, the conductivity, specific capacity, mechanical property and the like of the battery are influenced, and even internal short circuit is caused, so that accidents such as fire and explosion occur.
The polymer electrolyte is a solid polymer material with ion conduction function and is an effective medium for ion transmission. In the lithium ion secondary battery, the lithium ion secondary battery is not only an electrolyte, but also plays a role in isolating and supporting a diaphragm, and has the advantages of good flame retardance, high flexibility, low design cost and the like. Polymer electrolytes are safer, more reliable, and more durable electrolyte systems than electrolytes. The polymer electrolyte may be classified into a double ion polymer electrolyte and a single ion polymer electrolyte according to conductive ions. In the polymer electrolyte studied at present, double ion conductors are common (such as Chinese patent CN109037774B, CN111769322A, CN111769320A, etc.), but concentration gradients are easy to form in the electrolyte, concentration polarization is generated, irreversible loss of energy density of the lithium ion battery is caused, and the battery performance is reduced. The single-ion polymer electrolyte can effectively solve the problem, namely the polymer electrolyte which is limited in anion movement and only provides lithium ions and has the conductivity, and has the advantages of having the ion migration number close to 1, effectively inhibiting lithium dendrites and the like. One of the common preparation means is to covalently bond the anion in the backbone or branch of the polymer. However, the single-ion polymer electrolyte still has the problems of low ionic conductivity, insufficient mechanical properties and the like, so that the practical application is limited, and the structural composition of the single-ion polymer electrolyte needs to be further designed and improved to improve the performance of the single-ion polymer electrolyte.
The design and synthesis of the novel single-ion polymer electrolyte with a two-phase structure enable the single-ion polymer electrolyte to have higher ionic conductivity and certain mechanical properties at the same time, and is an important development direction of the single-ion polymer electrolyte. The Chinese patent with the application publication number of CN111326788A discloses a segmented copolymer obtained by polymerizing three monomers, namely lithium salt containing a p-styrenesulfonyl group, UPyMA containing quadruple hydrogen bonds and polyethylene glycol monomethyl ether methacrylate, and has excellent ion migration number and ion conductivity as a single-ion polymer electrolyte. But it is prepared by using reversible addition-fragmentation chain transfer polymerization, and the synthesis process is complex. Polyurethane is a typical high polymer material with a two-phase structure, and a carbamate bond and a ureido in the structure of the polyurethane can form a hydrogen bond structure to serve as a physical cross-linking agent to push the polymer to undergo microphase separation to form a two-phase structure with soft and hard segments. For the polyurethane single-ion polymer electrolyte, the hard segment can play a supporting role to provide certain mechanical strength, the soft segment still keeps a lower glass transition temperature, the transmission of lithium ions is facilitated, and the polyurethane single-ion polymer electrolyte can be expected to have excellent conductivity and certain mechanical property and excellent comprehensive performance.
Fluorine is the most electronegative element among known elements, and perfluoroalkyl is an electron withdrawing group having a strong negative charge delocalization. Therefore, lithium salts with perfluoroalkyl groups tend to have low lattice energy, which can effectively reduce the interaction between cations and anions, resulting in electrolyte systems with a greater proportion of available carriers and higher ionic conductivity, which is very advantageous for minimizing ohmic losses in lithium ion batteries. Chinese patent application publication No. CN108091930a discloses a novel single-ion polymer electrolyte containing fluorine-containing functional monomer prepared by radiation grafting method, which has excellent comprehensive properties. After a small amount of plasticizer is added, the room temperature conductivity can reach 10 -5 S·cm -1 。
Patent CN108832178B proposes a polyester/polyurethane single-ion polymer electrolyte having a two-phase structure, which has both a certain conductivity and film forming property. Although such a single-ion polymer electrolyte having a two-phase structure can achieve a certain compromise between mechanical strength and conductivity, since most lithium ions are in an ion-associated state, they cannot participate in an ion transport process as effective carriers, so that the conductivity thereof is low.
In summary, the single-ion polymer electrolyte has the problems of insufficient ion conductivity, excellent ion conductivity, certain mechanical properties, and the like, and greatly limits the practical application thereof.
Disclosure of Invention
The invention aims to solve the problems that the traditional single-ion polymer electrolyte cannot have both lower glass transition temperature and higher lithium ion concentration and cannot have excellent ion conductivity and mechanical property, and provides a fluorine-containing polyurethane single-ion polymer electrolyte membrane, a preparation method and application thereof.
The chemical structural formula of the fluorine-containing polyurethane single-ion polymer electrolyte membrane is shown as follows:
in the above formula, p is an integer of 2 to 110.
The preparation method of the fluorine-containing polyurethane single-ion polymer electrolyte membrane comprises the following steps:
1. under the protection of inert gas atmosphere, adding lithium isophthalic acid-5-sulfonate and polyethylene oxide into a solvent, reacting for 12-94 hours at the temperature of 70-200 ℃, and then carrying out vacuum water removal treatment to obtain a reactant a, wherein the molar ratio of the lithium isophthalic acid-5-sulfonate to the polyethylene oxide is 1:2.01;
2. reactant a obtained in step one, a perfluoro alkyl diamine (structure such as R 2 ) And diisocyanates (structure as R 1 ) Adding the mixture into a solvent, and reacting for 12-94 hours at the temperature of 30-100 ℃ to obtain a polymerization product, wherein the mol ratio of the reactant a to the perfluoroalkyl diamine to the diisocyanate is 1 (0.01-1) (1.01-2);
3. washing the polymerization product obtained in the second step with water, washing with alcohol and drying to obtain the fluorine-containing polyurethane single-ion polymer electrolyte; and adding the fluorine-containing polyurethane single-ion polymer electrolyte into a solvent, and performing film forming treatment to obtain the fluorine-containing polyurethane single-ion polymer electrolyte film.
The application of the fluorine-containing polyurethane single-ion polymer electrolyte membrane is that the fluorine-containing polyurethane single-ion polymer electrolyte membrane is used as an electrolyte material in an all-solid-state polymer lithium ion battery.
For the single ion polymer electrolyte, the aim of improving conductivity is mainly achieved by improving the effective carrier concentration and carrier migration speed, and the main method comprises the steps of designing and adjusting an anion structure to reduce the binding energy of anions and cations, reduce the glass transition temperature of the polymer and the like. The lower glass transition temperature and the higher lithium ion concentration are difficult to be combined, so that the improvement of the conductivity of the electrolyte is limited. Meanwhile, in order to realize the assembly and practical application of the polymer lithium ion battery, the single ion polymer electrolyte needs to have film forming property and certain mechanical strength.
The polyurethane has a two-phase structure with soft and hard segments, and the polyurethane single-ion conductor prepared by introducing the urethane structure into the single-ion polymer electrolyte main chain can balance the contradiction between the ionic conductivity and the mechanical property. In order to further improve the conductivity, the purpose of improving the effective carrier concentration of the polyurethane single-ion conductor to improve the ion conductivity of the polyurethane single-ion conductor can be achieved by introducing a perfluoroalkyl group with strong negative charge delocalization function into a hard segment, so that the fluorine-containing polyurethane single-ion conductor with excellent comprehensive performance is prepared.
The principle of the invention is as follows:
1. the polymer is of a polyurea polyurethane structure, and the ureido can form a hydrogen bond with a planar double-bifurcation structure, so that strong cohesive force of a hard segment micro-area is generated, and the film forming property and the mechanical strength of the polyurethane single-ion polymer electrolyte film are effectively improved. The introduction of urea groups can significantly improve the strength and elasticity of the membrane, and the reactivity of the polymer is also improved. Whereas the urethane group of the polyurethane structure of CN108832178B of the background art has only one active hydrogen atom, only one single ligand hydrogen bond is formed.
2. The perfluoroalkyl is introduced into the hard segment containing the anion structure of the polymer, has strong charge delocalization effect, and can effectively improve the dissociation of lithium ions. The polyurethane single ion polymer electrolyte in patent CN108832178B affects the effective carrier concentration of the electrolyte due to its regular structure, having ionic aggregates. Compared with the method, the method has the advantages that the effective carrier concentration in the system is obviously improved through the introduction of the perfluoroalkyl in the hard segment, so that the conductivity of the fluorine-containing polyurethane single-ion polymer electrolyte is obviously improved.
It can be seen that the polymer of the present invention is structurally greatly modified compared to the CN108832178B patent, so that the mechanical properties (including strength and flexibility) and the electrical conductivity are greatly improved.
The invention has the beneficial effects that:
(1) According to the preparation method of the fluorine-containing polyurethane single-ion polymer electrolyte membrane, the prepared fluorine-containing polyurethane single-ion polymer electrolyte can form a two-phase structure, wherein a hard segment containing an anion structure has a supporting effect, a hydrogen bond structure with a physical crosslinking effect can be formed, and the film forming property and the mechanical property of the polymer are improved; the soft section can keep a lower vitrification temperature, plays a role in carrier transmission, and effectively relieves the contradiction between the conductivity and the mechanical property of the single-ion polymer electrolyte.
The invention has hard segments with benzenesulfonic acid as anions, perfluoroalkyl groups and hydrogen bond structures, and is randomly dispersed in a continuous soft phase with low glass transition temperature; meanwhile, for the polyurethane single-ion polymer electrolyte with anions distributed in the hard segment, the lithium ion concentration can be changed in a larger range while the glass transition temperature of the soft segment is kept low by adjusting the proportion of the soft segment and the hard segment, so that the problem that the traditional single-ion polymer electrolyte cannot have both the lower glass transition temperature and the higher lithium ion concentration is effectively solved.
The fluorine-containing polyurethane single-ion polymer electrolyte is a random copolymer, and urea groups capable of forming hydrogen bonds with planar double-bifurcation structures are introduced, so that the three-dimensional structure can generate strong cohesive force of hard segment micro-areas, and the film forming property and mechanical strength of the polyurethane single-ion polymer electrolyte film are effectively improved.
(2) The fluorine-containing polyurethane single-ion polymer electrolyte prepared by the invention can effectively improve the dissociation degree of lithium ions and improve the effective carrier concentration in an electrolyte system by introducing a perfluoroalkyl structure with strong charge delocalization function into a hard segment containing an anion structure in the system. The fluorine-containing single-ion polymer electrolyte with high lithium salt concentration, low glass transition temperature, excellent electric conductivity and certain mechanical property is prepared.
(3) The fluorine-containing polyurethane single-ion polymer electrolyte prepared by the invention has the advantages of simple synthesis method, cheap and easily available raw materials, high room temperature conductivity, low glass transition temperature, good film forming performance, high lithium ion migration number, wide electrochemical window, good thermal stability and the like, and has potential application value in the aspect of lithium ion batteries.
The invention can obtain the fluorine-containing polyurethane single-ion polymer electrolyte membrane, and the preparation method and the application thereof.
Drawings
FIG. 1 is an infrared spectrum of a fluorine-containing polyurethane single-ion polymer electrolyte obtained in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the fluorine-containing polyurethane single-ion polymer electrolyte obtained in example 1;
FIG. 3 is a complex plan view of impedance of the fluorine-containing polyurethane single-ion polymer electrolyte membrane obtained in example 1;
FIG. 4 is an enlarged view of the high frequency region of the impedance complex plan view of the fluorine-containing polyurethane single-ion polymer electrolyte membrane obtained in example 1;
FIG. 5 is Li/LiFePO assembled with the fluoropolymer electrolyte membrane of example 1 as the electrolyte 4 Charge-discharge curve of the battery at 0.1C at room temperature.
Detailed Description
The first embodiment is as follows: the chemical structural formula of the fluorine-containing polyurethane single-ion polymer electrolyte membrane is shown as follows:
in the above formula, p is an integer of 2 to 110.
The second embodiment is as follows: the preparation method of the fluorine-containing polyurethane single-ion polymer electrolyte membrane comprises the following steps:
1. under the protection of inert gas atmosphere, adding lithium isophthalic acid-5-sulfonate and polyethylene oxide into a solvent, reacting for 12-94 hours at the temperature of 70-200 ℃, and then carrying out vacuum water removal treatment to obtain a reactant a, wherein the molar ratio of the lithium isophthalic acid-5-sulfonate to the polyethylene oxide is 1:2.01;
2. reactant a obtained in step one, a perfluoro alkyl diamine (structure such as R 2 ) And diisocyanates (structure as R 1 ) Adding the mixture into a solvent, and reacting for 12-94 hours at the temperature of 30-100 ℃ to obtain a polymerization product, wherein the mol ratio of the reactant a to the perfluoroalkyl diamine to the diisocyanate is 1 (0.01-1) (1.01-2);
3. washing the polymerization product obtained in the second step with water, washing with alcohol and drying to obtain the fluorine-containing polyurethane single-ion polymer electrolyte; and adding the fluorine-containing polyurethane single-ion polymer electrolyte into a solvent, and performing film forming treatment to obtain the fluorine-containing polyurethane single-ion polymer electrolyte film.
The specific reaction equation for obtaining the fluorine-containing polyurethane single-ion polymer electrolyte in the embodiment is as follows:
the beneficial effect of this embodiment is:
(1) According to the preparation method of the fluorine-containing polyurethane single-ion polymer electrolyte membrane, the prepared fluorine-containing polyurethane single-ion polymer electrolyte can form a two-phase structure, wherein a hard segment containing an anion structure has a supporting effect, a hydrogen bond structure with a physical crosslinking effect can be formed, and the film forming property and the mechanical property of the polymer are improved; the soft section can keep a lower vitrification temperature, plays a role in carrier transmission, and effectively relieves the contradiction between the conductivity and the mechanical property of the single-ion polymer electrolyte.
The present embodiment has hard segments of benzenesulfonic acid as anions, perfluoroalkyl groups, and hydrogen bond structures, randomly dispersed in a continuous soft phase with low glass transition temperature; meanwhile, for the polyurethane single-ion polymer electrolyte with anions distributed in the hard segment, the lithium ion concentration can be changed in a larger range while the glass transition temperature of the soft segment is kept low by adjusting the proportion of the soft segment and the hard segment, so that the problem that the traditional single-ion polymer electrolyte cannot have both the lower glass transition temperature and the higher lithium ion concentration is effectively solved.
The fluorine-containing polyurethane single-ion polymer electrolyte is a random copolymer, and urea groups capable of forming hydrogen bonds with planar double-bifurcation structures are introduced, so that the three-dimensional structure can generate strong cohesive force of hard segment micro-areas, and the film forming property and mechanical strength of the polyurethane single-ion polymer electrolyte film are effectively improved.
(2) The fluorine-containing polyurethane single-ion polymer electrolyte prepared by the embodiment can effectively improve the dissociation degree of lithium ions and improve the effective carrier concentration in an electrolyte system by introducing a perfluoroalkyl structure with strong charge delocalization function into a hard segment containing an anion structure in the system. The fluorine-containing single-ion polymer electrolyte with high lithium salt concentration, low glass transition temperature, excellent electric conductivity and certain mechanical property is prepared.
(3) The fluorine-containing polyurethane single-ion polymer electrolyte prepared by the embodiment has the advantages of simple synthesis method, cheap and easily available raw materials, high room temperature conductivity, low glass transition temperature, good film forming performance, high lithium ion migration number, wide electrochemical window, good thermal stability and the like, and has potential application value in the aspect of lithium ion batteries.
And a third specific embodiment: the second difference between this embodiment and the specific embodiment is that: in the first step, lithium isophthalic acid-5-sulfonate and polyethylene oxide with molecular weight of 1500 are added into a solvent under the protection of nitrogen atmosphere, reacted for 72 hours at the temperature of 150 ℃, and then treated for 2 hours by vacuum water removal at the temperature of 120 ℃ to obtain a reactant a.
The other steps are the same as those of the second embodiment.
The specific embodiment IV is as follows: the difference between this embodiment and the second or third embodiment is that: in the second step, the reactant a, the perfluoroalkyl diamine and the diisocyanate are added into a solvent to react for 72 hours at the temperature of 70 ℃ to obtain a polymerization product, wherein the reactant a is obtained.
The other steps are the same as those of the second or third embodiment.
Fifth embodiment: the second to fourth embodiments differ from the present embodiment in that: the perfluoroalkyl-containing diamine (structure as R 2 ) Is 3, 5-bis (trifluoromethyl) -1, 2-phenylenediamine, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether or 2, 2-bis [4- (4-aminophenoxy benzene) hexafluoropropane]。
Other steps are the same as those of the second to fourth embodiments.
Specific embodiment six: the present embodiment differs from the second to fifth embodiments in that: the diisocyanate (structure as R 1 ) Is p-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylylene diisocyanate, 4' -methylenebis (phenyl isocyanate) or hexamethylene diisocyanate.
Other steps are the same as those of the second to fifth embodiments.
Seventh embodiment: the present embodiment differs from the second to sixth embodiments in that: the solvent in the first to third steps is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
Other steps are the same as those of the second to sixth embodiments.
Eighth embodiment: the present embodiment differs from the second to seventh embodiments in that: and step three, drying, namely placing the dried product in a vacuum drying oven after purging, and drying the dried product at 80 ℃ for 48 hours.
The other steps are the same as those of the second to seventh embodiments.
Detailed description nine: the present embodiment differs from the second to eighth embodiments in that: the film forming method in the third step is a solution casting method film forming or a hot pressing method film forming, and the thickness of the fluorine-containing polyurethane single-ion polymer electrolyte film is 0.005-2 mm.
Other steps are the same as those of embodiments two to eight.
Detailed description ten: the application of the fluorine-containing polyurethane single-ion polymer electrolyte membrane in the embodiment is that the fluorine-containing polyurethane single-ion polymer electrolyte membrane is used as an electrolyte material in an all-solid-state polymer lithium ion battery.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the fluorine-containing polyurethane single-ion polymer electrolyte membrane comprises the following steps:
1. under the protection of nitrogen atmosphere, adding 0.464g of lithium isophthalic acid-5-sulfonate and 5.547g of polyethylene oxide (molecular weight 1500) into 60mL of N-methylpyrrolidone (NMP) solvent according to the molar ratio of 1:2.01, reacting for 72h at the temperature of 150 ℃, and then carrying out vacuum dehydration treatment for 2h at the temperature of 120 ℃ to obtain a reactant a;
2. adding the reactant a obtained in the step one, 0.239g of 2, 2-bis [4- (4-aminophenoxy benzene) hexafluoropropane ] and 0.373g of terephthal-ylene diisocyanate into 60mL of NMP solvent according to the mol ratio of 9:1:10, and reacting for 72 hours at the temperature of 70 ℃ to obtain a polymerization product;
3. washing the polymerization product obtained in the second step with water, washing with alcohol, placing in a vacuum drying oven after purging, and drying at 80 ℃ for 48 hours to obtain the fluorine-containing polyurethane single-ion polymer electrolyte;
4. and adding 0.2g of the prepared fluorine-containing polyurethane single-ion polymer electrolyte into 5mL of DMF solvent, stirring for 2h to ensure full dissolution, casting into a polytetrafluoroethylene mould, and performing variable-temperature drying to form a film to obtain the fluorine-containing polyurethane single-ion polymer electrolyte membrane.
The thickness of the fluorine-containing polyurethane single-ion polymer electrolyte membrane prepared in the example is 0.17mm, and the conductivity at room temperature is 5.76X10 -7 S·cm -1 The breaking stress is 9.82MPa, and the fluorine-containing polyurethane single-ion polymer electrolyte membrane is used for Li/LiFePO assembled by electrolyte 4 The discharge capacity of the battery was 141mAh g -1 。
The method for testing the conductivity of the polymer electrolyte is as follows: the prepared fluorine-containing polyurethane single-ion polymer electrolyte membrane is clamped between two stainless steel sheets with the diameter of 1cm to form a polymer electrolyte blocking electrode system, and the bulk impedance of a sample is obtained through an alternating current impedance test. The ion conductivity of the electrolyte is calculated from the relationship between the bulk impedance (Rb) and the ion conductivity (σ), and the calculation formula is as follows:
where d is the polymer electrolyte membrane thickness, and S is the contact area of the stainless steel electrode and the polymer electrolyte.
Fig. 1 is an infrared spectrum of the fluorine-containing polyurethane single-ion polymer electrolyte obtained in this example, and as shown in fig. 1, this example successfully prepares the designed fluorine-containing polyurethane single-ion polymer electrolyte with high carrier concentration. FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the fluorine-containing polyurethane single-ion polymer electrolyte obtained in the embodiment, and as shown in FIG. 2, the reaction in the embodiment is complete, and the fluorine-containing polyurethane single-ion polymer electrolyte with a designed proportion is successfully prepared. Fig. 3 is a complex plan view of impedance of the fluorine-containing polyurethane single-ion polymer electrolyte membrane obtained in this example. FIG. 4 is an enlarged view of the high frequency region of the impedance complex plane view of the fluorine-containing polyurethane single-ion polymer electrolyte membrane obtained in this example, which was calculated to give a room temperature conductivity of 5.76X10 -7 S·cm -1 . FIG. 5 is a Li/LiFePO electrolyte film assembled with the fluoropolymer electrolyte membrane obtained in this example 4 The battery has excellent discharge capacity and coulombic efficiency as shown in fig. 5, with a charge-discharge curve at 0.1C at room temperature.
Example 2: the preparation method of the fluorine-containing polyurethane single-ion polymer electrolyte membrane comprises the following steps:
1. under the protection of nitrogen atmosphere, adding 0.464g of lithium isophthalic acid-5-sulfonate and 5.547g of polyethylene oxide (molecular weight 1500) into 60mL of N-methylpyrrolidone (NMP) solvent according to the molar ratio of 1:2.01, reacting for 72h at the temperature of 150 ℃, and then carrying out vacuum dehydration treatment for 2h at the temperature of 120 ℃ to obtain a reactant a;
2. adding the reactant a obtained in the step one, 0.239g of 2, 2-bis [4- (4-aminophenoxy benzene) hexafluoropropane ] and 0.373g of terephthal-ylene diisocyanate into 60mL of NMP solvent according to the mol ratio of 9:1:10, and reacting for 72 hours at the temperature of 70 ℃ to obtain a polymerization product;
3. washing the polymerization product obtained in the second step with water, washing with alcohol, placing in a vacuum drying oven after purging, and drying at 80 ℃ for 48 hours to obtain the fluorine-containing polyurethane single-ion polymer electrolyte;
4. the fluorine-containing polyurethane single-ion polymer electrolyte membrane is prepared by forming a film by a hot-pressing method at the pressure of 15MPa and the temperature of 90 ℃.
The fluorine-containing single-ion polymer electrolyte membrane prepared in the example has the thickness of 0.09mm and the conductivity of 2.73X10 at room temperature -7 S·cm -1 The breaking stress was 11.83MPa.
Claims (6)
1. The preparation method of the fluorine-containing polyurethane single-ion polymer electrolyte membrane is characterized by comprising the following steps:
1. under the protection of nitrogen atmosphere, adding lithium isophthalic acid-5-sulfonate and polyethylene oxide into a solvent, reacting at a temperature of 150 ℃ for 72h, and then carrying out vacuum water removal treatment for 2h to obtain a reactant a, wherein the molar ratio of the lithium isophthalic acid-5-sulfonate to the polyethylene oxide is 1:2.01;
2. adding the reactant a, the perfluoroalkyl diamine and the diisocyanate obtained in the step one into a solvent, and reacting for 12-94 hours at the temperature of 30-100 ℃ to obtain a polymerization product, wherein the molar ratio of the reactant a, the perfluoroalkyl diamine and the diisocyanate is 1 (0.01-1): (1.01-2);
the perfluoroalkyl-containing diamine in the second step is 3, 5-bis (trifluoromethyl) -1, 2-phenylenediamine, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether or 2, 2-bis [4- (4-aminophenoxy benzene) hexafluoropropane ];
the diisocyanate in the second step is p-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylylene diisocyanate, 4' -methylenebis (phenyl isocyanate) or hexamethylene diisocyanate;
3. washing the polymerization product obtained in the second step with water, washing with alcohol and drying to obtain the fluorine-containing polyurethane single-ion polymer electrolyte; adding the fluorine-containing polyurethane single-ion polymer electrolyte into a solvent, and performing film forming treatment to obtain the fluorine-containing polyurethane single-ion polymer electrolyte film which is used as an electrolyte material in an all-solid-state polymer lithium ion battery.
2. The method for preparing a fluorine-containing polyurethane single-ion polymer electrolyte membrane according to claim 1, wherein in the second step, a reactant a, a perfluoroalkyl diamine and diisocyanate are added into a solvent, and the mixture is reacted at a temperature of 70 ℃ for 72h to obtain a polymerization product.
3. The method for producing a fluorine-containing polyurethane single-ion polymer electrolyte membrane according to claim 1, wherein the solvent in the step one to three is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
4. The method for producing a fluorine-containing polyurethane single-ion polymer electrolyte membrane according to claim 1, wherein the drying in the third step is performed by placing the membrane in a vacuum drying oven after purging, and drying 48h at 80 ℃.
5. The method for preparing the fluorine-containing polyurethane single-ion polymer electrolyte membrane according to claim 1, wherein the film forming method in the third step is a solution casting method film forming or a hot pressing method film forming, and the thickness of the fluorine-containing polyurethane single-ion polymer electrolyte membrane is 0.005-2 mm.
6. The fluorourethane single-ion polymer electrolyte membrane prepared by the method of claim 1.
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